CN112885618B - Porous carbon electrode material loaded with metal oxide and preparation method thereof - Google Patents
Porous carbon electrode material loaded with metal oxide and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 30
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 238000000967 suction filtration Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 230000010355 oscillation Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000013077 target material Substances 0.000 claims abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 7
- 238000004146 energy storage Methods 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 4
- 238000007654 immersion Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000011148 porous material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- -1 metal oxide modified activated carbon Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a porous carbon electrode material loaded with metal oxide and a preparation method thereof, wherein the preparation method comprises the following steps: A. putting activated carbon powder into a hydrochloric acid solution with 8-10% volume concentration, heating and refluxing for 4-6h, and drying a precipitate obtained by suction filtration; B. b, stirring the material obtained in the step A with deionized water, washing with water, and drying the precipitate obtained by suction filtration to obtain an activated carbon material; C. placing the activated carbon material obtained in the step B into a container, carrying out metal ion modification by adopting a vacuum oscillation isovolumetric immersion method, and carrying out 0.03-0.1 mol/LFeCl treatment by using a burette3Dropping the water solution in a vacuumized state and keeping shaking to obtain a paste-state mixture, then carrying out ultrasonic treatment for 1-3h at 25-60 ℃, then drying for 5-8h in a vacuum state at 110-120 ℃, and finally heating in a tube furnace to 400-450 ℃ for sintering for 2-4h, wherein the sintering atmosphere is an inert atmosphere, thus obtaining the target material. The electrode prepared by the method improves the energy storage of the super capacitor under the condition of basically not changing the surface structure of the original active carbon.
Description
Technical Field
The invention relates to the field of preparation of electrode materials of super capacitors, in particular to a porous carbon electrode material loaded with metal oxides and a preparation method thereof.
Background
The energy storage of the conventional activated carbon-based supercapacitor is mostly limited by the theory of double electric layers. According to the theory of the electric double layer, the specific capacity of the activated carbon material is in direct proportion to the specific surface area, namely, the larger the specific surface area is, the larger the specific capacity is. When the specific surface area of the activated carbon material used is not high, the specific capacitance that can be contributed by the activated carbon material is extremely limited, so that the energy density of the activated carbon-based supercapacitor is also low. In addition, the surface modification performance of the general activated carbon material is difficult to be uniformly loaded, and agglomeration is easy to generate, so that the performance of the electrode material is greatly influenced.
Disclosure of Invention
In view of this, the present invention provides a porous carbon electrode material loaded with metal oxide and a preparation method thereof, so as to solve the above technical problems.
The technical scheme of the invention is realized as follows: a preparation method of a porous carbon electrode material loaded with metal oxide comprises the following steps:
A. putting activated carbon powder into a hydrochloric acid solution with 8-10% volume concentration, heating and refluxing for 4-6h, and drying a precipitate obtained by suction filtration; the ash and impurities in the activated carbon material are removed in the step, so that the introduction of the impurity ions brought by the later loading is prevented; heating and refluxing for 4-6h to remove impurities difficult to remove in the activated carbon by hydrochloric acid solution, and avoiding long-time use of hydrochloric acid pickling to prevent influence of other oxygen-containing functional groups on the surface chemical properties of the activated carbon;
B. b, stirring the material obtained in the step A by using deionized water, washing by using water, and drying the precipitate obtained by suction filtration to obtain an activated carbon material; the step removes acid solution or ions remained on the surface of the activated carbon in the acid washing process, thereby avoiding the influence on the subsequent metal ion doping caused by the change of the acid-base property of the material surface by acid washing;
C. placing the activated carbon material obtained in the step B into a container, and using a burette to make the concentration of 0.03-0.1 mol/LFeCl3Dropping the aqueous solution in a vacuum state and keeping shaking to obtain a mixture in a paste state, and then performing ultrasonic treatment at 25-60 ℃ for 1-3h, wherein FeCl is easily caused if the ultrasonic temperature is too high3Hydrolyzing; then drying for 5-8h under the vacuum state at the temperature of 110-120 ℃, wherein the drying temperature is too high and the iron oxide and the like are easy to convert; and finally, heating to 400-450 ℃ in a tube furnace, and sintering for 2-4h in an inert atmosphere to obtain the target material.
Wherein, a vacuum oscillation isometric impregnation method is adopted, namely the volume of the metal ion solution impregnated on the surface of the activated carbon is consistent with the pore volume of the activated carbon material, and the pore volume is analyzed by a BET model to obtain a value estimated from the specific surface area and the pore size distribution; maintaining a vacuum state and uniformly distributing by oscillation in the dipping process, and performing a subsequent uniform dispersion process of constant-temperature ultrasound; controlling the volume of the flowing metal ionic liquid and the dropping speed of the liquid in the vacuum impregnation process by using a burette, and further controlling the state of the impregnated active carbon; in a vacuum state, air on the surface of the activated carbon and in the pore channels is extracted from the surface of the activated carbon so that the metal ionic liquid can be fully immersed into the surface of the activated carbon; the oscillation operation ensures that the metal ionic liquid is uniformly distributed when being immersed into the surface of the carbon material in the dipping process, so that the phenomenon of agglomeration of the metal oxide for subsequent sintering is reduced; heating and ultrasonically treating the metal ion solution soaked into the surface of the activated carbon under a certain temperature condition, and fully and uniformly dispersing the metal ion solution again under the action of thermal diffusion to reduce the local agglomeration phenomenon; sintering in inert atmosphere to ensure that the activated carbon is not oxidized during sintering.
Further, in the step A, the mass volume ratio kg/L of the activated carbon to the hydrochloric acid solution is 1: 200-500, preferably 1: 200.
further, in the step B, the mass volume ratio kg/L of the materials to the deionized water is 1: 500-1000, preferably 1: 500.
further, in the step A, the volume concentration of the hydrochloric acid solution is 10%.
Further, in the step B, the washing time is 5-12h, preferably 12 h.
Further, in the step B, the temperature of the deionized water is 25-95 ℃, and preferably 25 ℃.
Further, in the step C, the ultrasonic temperature is 60 ℃ and the time is 1 h.
Further, in the step C, the sintering temperature is 400 ℃, and the sintering time is 2 hours.
Further, in the step C, the inert atmosphere is Ar with the flow rate of 180 ml/min.
The invention discloses a porous carbon electrode material loaded with metal oxide, which is prepared by the preparation method of the porous carbon electrode material loaded with metal oxide.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention firstly uses hydrochloric acid with a certain concentration to wash activated carbon powder, then carries out water washing, and then uses FeCl3Loading the solution to the living body by vacuum equal-volume impregnation methodThe surface and the pore canal of the charcoal are kept in a vacuum state and uniformly distributed by oscillation in the dipping process, and the novel Fe is prepared and obtained in the subsequent uniform dispersion process of constant temperature ultrasound3O4-an AC electrode. The electrode prepared by the method improves the energy storage of the super capacitor under the condition of basically not changing the surface structure of the original active carbon. Compared with the traditional activated carbon-based supercapacitor, the invention utilizes a vacuum oscillation isovolumetric impregnation method to load metal oxide on the surface of activated carbon, so that the storage of redox capacitance is increased in the existing physical adsorption and desorption aspect, and the specific capacitance is improved under the condition of long cycle life. And the metal oxide is uniformly dispersed on the surface of the activated carbon, so that the influence of volume expansion of the agglomerated metal oxide in circulation is reduced, and a stable circulation performance is provided.
According to the method, hydrochloric acid solution with a certain concentration is heated and refluxed for acid washing, so that ash and impurities in the activated carbon material are removed, and introduction of foreign ions caused by later loading is prevented; however, the pickling concentration is high, the specific surface structure of the material is easily damaged in the pickling process, a certain amount of micropores can be reduced after the loading, and the specific capacitance is reduced. In addition, FeCl with a certain concentration is controlled3Solutions, such as those with too high a concentration, yield poor results in terms of the specific surface of the material.
Drawings
FIG. 1 is a TEM, HRTEM and EDS image of an activated carbon as it is after washing and before modification.
FIG. 2 is a water washed, unmodified activated carbon as received (AC) and N of metal oxide modified activated carbon of example 1(AC-0.03M), example 2(AC-0.05M), example 3(AC-0.1M)2Adsorption and desorption curve chart.
FIG. 3 is a graph showing the specific capacitance of activated carbon as it is (AC) after washing and before modification, in example 1(AC-0.03M), example 2(AC-0.05M) and example 3 (AC-0.1M).
It can be seen that the loading on the surface of the activated carbon is more uniform, the adsorption type is IV-type adsorption, and the specific capacitance is increased along with the increase of the doping concentration.
Detailed Description
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention can be obtained commercially without specific description.
Example 1
A. Putting 8g of activated carbon powder into a hydrochloric acid solution with the volume concentration of 10%, wherein the mass volume ratio kg/L of the activated carbon to the hydrochloric acid solution is 1: 200 of a carrier; heating and refluxing at 25-50 deg.C for 5 hr, and oven drying the precipitate obtained by suction filtration;
B. and B, stirring and washing the material obtained in the step A with deionized water at 25 ℃ for 12h, wherein the mass volume ratio kg/L of the material to the deionized water is 1: 500, a step of; drying the precipitate obtained by suction filtration, and repeating the drying for 3 times to obtain an activated carbon material;
C. placing the activated carbon material obtained in the step B into a filter flask, and using a burette to mix 0.03M FeCl3Slowly dropping 10ml of aqueous solution into a suction filter flask in a vacuum state and keeping shaking to obtain a paste mixture, then ultrasonically dipping for 1h at 60 ℃, drying for 5h in a vacuum state at 120 ℃, finally heating to 400 ℃ in a tubular furnace and sintering for 2h in Ar atmosphere, wherein the flow rate of introducing Ar is 180ml/min, thus obtaining the porous carbon electrode material loaded with metal oxide.
The electrode material prepared in example 1 was examined for specific surface area and specific capacitance. The specific surface structure and the pore size distribution are not greatly changed, and the specific capacitance can obtain 6F g-1The improvement of (1). In the embodiment 1, the metal ion solution forms metal oxide on the surface of the activated carbon through sintering on the surface and in the pore channels of the activated carbon, and redox electrolyte ion storage is added on the surface of the electric double layer in the charging and discharging processes, so that the effect of improving the specific capacitance is achieved.
Example 2
A. Putting 8g of activated carbon powder into a hydrochloric acid solution with the volume concentration of 10%, wherein the mass volume ratio kg/L of the activated carbon to the hydrochloric acid solution is 1: 200 of a carrier; heating and refluxing at 25-50 deg.C for 5 hr, and oven drying the precipitate obtained by suction filtration;
B. and B, stirring and washing the material obtained in the step A with deionized water at 25 ℃ for 12h, wherein the mass volume ratio kg/L of the material to the deionized water is 1: 500, a step of; drying the precipitate obtained by suction filtration, and repeating the drying for 3 times to obtain an activated carbon material;
C. placing the activated carbon material obtained in the step B into a filter flask, and using a burette to mix 0.05M FeCl3Slowly dropping 10ml of aqueous solution into a suction filter flask in a vacuum state and keeping shaking to obtain a paste mixture, then ultrasonically dipping for 1h at 60 ℃, drying for 5h in a vacuum state at 120 ℃, finally heating to 400 ℃ in a tubular furnace and sintering for 2h in Ar atmosphere, wherein the flow rate of introducing Ar is 180ml/min, thus obtaining the porous carbon electrode material loaded with metal oxide.
The electrode material prepared in example 2 was examined for specific surface area and specific capacitance. The specific surface structure and the pore size distribution do not change greatly, and the specific capacitance can obtain 12Fg-1The improvement of (1). The higher concentration of the metal solution in example 2 compared to that in example 1 favors the formation of more metal oxide on the surface of the activated carbon and increases the energy storage of more redox.
Example 3
A. Putting 8g of activated carbon powder into a hydrochloric acid solution with the volume concentration of 10%, wherein the mass volume ratio kg/L of the activated carbon to the hydrochloric acid solution is 1: 200 of a carrier; heating and refluxing at 25-50 deg.C for 5 hr, and oven drying the precipitate obtained by suction filtration;
B. and B, stirring and washing the material obtained in the step A with deionized water at 25 ℃ for 12h, wherein the mass volume ratio kg/L of the material to the deionized water is 1: 500, a step of; drying the precipitate obtained by suction filtration, and repeating for 3 times to obtain an activated carbon material;
C. placing the activated carbon material obtained in the step B into a filter flask, and using a burette to mix 0.1M FeCl3Slowly dropping 10ml of aqueous solution into a suction filter flask in a vacuum state and keeping shaking to obtain a paste mixture, then ultrasonically dipping for 1h at 60 ℃, drying for 5h in a vacuum state at 120 ℃, finally heating to 400 ℃ in a tubular furnace and sintering for 2h in Ar atmosphere, wherein the flow rate of introducing Ar is 180ml/min, thus obtaining the porous carbon electrode material loaded with metal oxide.
The electrode material obtained in example 3 was examined for specific surface area and specific capacitance, which resulted in 29Fg-1The improvement of (1). The metal ion solution in example 3 has a higher concentration than the former two, and forms more metal oxides to generate redox energy storage, but the modified activated carbon with a high concentration can block the micropores of the activated carbon to a certain extent.
Example 4
A. Putting 8g of activated carbon powder into a hydrochloric acid solution with 8% volume concentration, wherein the mass-volume ratio kg/L of the activated carbon to the hydrochloric acid solution is 1: 500, a step of; heating and refluxing at 25-50 deg.C for 4 hr, and oven drying the precipitate obtained by suction filtration;
B. b, stirring and washing the material obtained in the step A with deionized water at 90 ℃ for 12 hours, wherein the mass volume ratio kg/L of the material to the deionized water is 1: 1000, parts by weight; drying the precipitate obtained by suction filtration, and repeating for 3 times to obtain an activated carbon material;
C. placing the activated carbon material obtained in the step B into a filter flask, and using a burette to mix 0.1M FeCl3Slowly dropping 10ml of aqueous solution into a suction filter flask in a vacuum state and keeping shaking to obtain a paste mixture, then ultrasonically dipping the mixture for 3 hours at 25 ℃, drying the mixture for 8 hours in a vacuum state at 110 ℃, finally heating the mixture to 450 ℃ in a tubular furnace and sintering the mixture for 4 hours in Ar atmosphere, and introducing Ar at the flow speed of 180ml/min to obtain the porous carbon electrode material loaded with metal oxide. The electrode material obtained in example 4 was examined for specific surface area and specific capacitance, which resulted in a specific capacitance of 25F g-1The improvement of (1).
Comparative example 1
8g of activated carbon powder was placed in a 12% strength by volume hydrochloric acid solution, and the other operations were substantially the same as in example 3. Comparative example 1 an electrode material was prepared for specific surface area and specific capacitance investigation, wherein the specific capacitance was reduced by 5F g-1. The pickling concentration in comparative example 1 is high, the specific surface structure is easily broken during pickling, a certain amount of micropores is reduced after loading, and the specific capacitance is reduced.
Comparative example 2
Based on example 3, FeCl was adjusted3The aqueous solution concentration was 0.5M and the other operations were substantially the same as in example 3. Comparative example 1 an electrode material was prepared for specific surface area investigation.
The results of the above examples and the comparative electrode materials were obtained from the following table 1:
| specific surface structure | Pore size of specific surface area (nm) | Specific capacitance (F g)-1) | |
| Activated carbon sample before modification | Micro-pores | 1503.9 | 147 |
| Example 1 | Micro-pores | 1676.81 | 153.3 |
| Example 2 | Micro-pores | 1621.04 | 159.2 |
| Example 3 | Micro-pores | 1586.46 | 176.8 |
| Example 4 | Micro-pores | 1518.52 | 172 |
| Comparative example 1 | The microporous structure is destroyed | 1544.32 | 142 |
| Comparative example 2 | The microporous structure is destroyed | 1208.19 | —— |
The above results show that examples 1 to 4 of the present invention are significantly improved in specific capacitance without large changes in specific surface structure and pore size distribution. The electrode prepared by the method improves the energy storage of the super capacitor under the condition of basically not changing the surface structure of the original active carbon.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a porous carbon electrode material loaded with metal oxide is characterized by comprising the following steps:
A. putting activated carbon powder into a hydrochloric acid solution with 8-10% volume concentration, heating and refluxing for 4-6h, and drying a precipitate obtained by suction filtration; the mass volume ratio kg/L of the activated carbon to the hydrochloric acid solution is 1: 200-500;
B. b, stirring the material obtained in the step A by using deionized water, washing by using water, and drying the precipitate obtained by suction filtration to obtain an activated carbon material;
C. c, placing the activated carbon material obtained in the step B into a container, carrying out metal ion modification by adopting a vacuum oscillation isovolumetric impregnation method, and carrying out 0.1mol/LFeCl modification by utilizing a burette3Dropping the water solution in a vacuumized state and keeping shaking to obtain a paste-state mixture, then carrying out ultrasonic treatment for 1-3h at 25-60 ℃, then drying for 5-8h in a vacuum state at 110-120 ℃, and finally heating in a tube furnace to 400-450 ℃ for sintering for 2-4h, wherein the sintering atmosphere is an inert atmosphere, thus obtaining the target material.
2. A method for preparing a porous carbon electrode material supporting a metal oxide as claimed in claim 1, characterized in that: in the step B, the mass volume ratio kg/L of the materials to the deionized water is 1: 500-1000.
3. A method of preparing a porous carbon electrode material supporting a metal oxide as claimed in claim 2, characterized in that: in the step A, the mass volume ratio kg/L of the activated carbon to the hydrochloric acid solution is 1: 200 of a carrier; in the step B, the mass volume ratio kg/L of the materials to the deionized water is 1: 500.
4. the method for producing a porous carbon electrode material supporting a metal oxide as claimed in claim 1, characterized in that: in the step A, the volume concentration of the hydrochloric acid solution is 10%.
5. The method for producing a porous carbon electrode material supporting a metal oxide as claimed in claim 1, characterized in that: in the step B, the washing time is 5-12 h.
6. The method for producing a metal oxide-supporting porous carbon electrode material according to claim 1 or 5, characterized in that: in the step B, the temperature of the deionized water is 25-95 ℃.
7. The method for producing a porous carbon electrode material supporting a metal oxide as claimed in claim 3, characterized in that: in the step C, the ultrasonic temperature is 60 ℃ and the ultrasonic time is 1 h.
8. The method for producing a porous carbon electrode material supporting a metal oxide as claimed in claim 3, characterized in that: in the step C, the sintering temperature is 400 ℃, and the sintering time is 2 hours.
9. The method for producing a porous carbon electrode material supporting a metal oxide as claimed in claim 1, characterized in that: in the step C, the inert atmosphere is Ar with the flow rate of 180 ml/min.
10. A porous carbon electrode material supporting a metal oxide, characterized by being produced by the method for producing a porous carbon electrode material supporting a metal oxide according to any one of claims 1 to 9.
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| CN105923634A (en) * | 2016-05-06 | 2016-09-07 | 海南大学 | Coconut-shell fiber-based activated carbon for supercapacitor and preparation method of activated carbon |
| CN109065371A (en) * | 2018-08-03 | 2018-12-21 | 东华大学 | A kind of flexible electrode and its preparation method and application |
| CN112086298A (en) * | 2020-09-17 | 2020-12-15 | 自然资源部天津海水淡化与综合利用研究所 | Modified activated carbon/ferroferric oxide composite material and preparation method and application thereof |
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| CN105293470A (en) * | 2015-11-12 | 2016-02-03 | 天津大学 | Template preparation method for hierarchical porous structure three-dimensional carbon nanometer net electrode material of supercapacitor |
| US11316148B2 (en) * | 2017-08-14 | 2022-04-26 | Sila Nanotechnologies, Inc. | Nanocomposite of a nanoporous material and an active material and method of synthesizing thereof |
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| CN105923634A (en) * | 2016-05-06 | 2016-09-07 | 海南大学 | Coconut-shell fiber-based activated carbon for supercapacitor and preparation method of activated carbon |
| CN109065371A (en) * | 2018-08-03 | 2018-12-21 | 东华大学 | A kind of flexible electrode and its preparation method and application |
| CN112086298A (en) * | 2020-09-17 | 2020-12-15 | 自然资源部天津海水淡化与综合利用研究所 | Modified activated carbon/ferroferric oxide composite material and preparation method and application thereof |
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| Coal tar residues-based nanostructured activated carbon/Fe3O4 composite electrode materials for supercapacitors;Yuhao Wang等;《J Solid State Electrochem》;20131030;1-8 * |
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